Ground-state and time-resolved infrared data are resented in the v(CO) region for [Re(LL)(CO)(4)](+) (LL is 2,2'-bipyridine (bpy), 4,4'-dimethyl-2,2'-bipyridine (dmb), or 1,10-phenanthroline (phen)) in 1,2-dichloroethane at 298 K following 354.7 nm excitation. The data demonstrate formation of a unique excited state for the [Re(LL)(CO)(4)](+) species followed by loss of a single carbonyl ligand to form a fac-Re(CO)(3) solvento complex.